SUPPORTING INFORMATION Table of Contents S1 1. General materials and methods S2 2. Syntheses of {Pd 84 } and {Pd 17 } S3-S4 3. MS studies of {Pd 84 }, {Pd 17 } and the two-component reactions S5-S6 4. Characterization of {Pd 84 }: IR, NMR, UV and TGA S7-S8 5. The hypothetical polyoxopalladate cluster, {Pd 60 } S9 6. Still + Legend for the assembly movie Pd Conversions (full).avi S9 7. References S9
1. General Materials and Methods All chemicals and solvents were used as purchased without further purification. Flame Atomic Absorption Spectroscopy Analysis: FAAS analysis was performed at the Environmental Chemistry Section, School of Chemistry, The University of Glasgow on a Perkin-Elmer 1100B Atomic Absorption Spectrophotometer. 1 H/ 31 P/ 13 C-Nuclear magnetic resonance spectroscopy ( 1 H/ 31 P/ 13 C-NMR): 1 H/ 31 P/ 13 C-NMR spectroscopy was performed on a Bruker DPX 400 spectrometer using the solvent signal as internal standard. All δ values are given in ppm. Infrared Spectroscopy: All IR experiments were carried out with a Shimadzu FTIR 8400S. Mass spectrometry: Measurements were made using a) Bruker micro ToFQ in negative ion mode; b) Waters Synapt G2 HDMS in sensitivity-mode equipped with a Quadrupole and Time-of-flight (Q/ToF) module for MSanalysis. Microanalysis: Carbon, nitrogen and hydrogen content were determined by the microanalysis services within the School of Chemistry, University of Glasgow using a EA 1110 CHNS, CE-440 Elemental Analyzer. Single Crystal X-Ray Diffraction: Single crystal datasets and unit cells were collected at 150(2) K on a Bruker Apex II Quasar diffractometer equipped with a graphite monochromator (λ (Mo Kα ) = 0.71 Å). Structure solution and refinement was carried out using SHELXL-97 1 and WinGX 2 via a full matrix least-squares on F 2 method 3. All non-hydrogen atoms were refined anisotropically unless otherwise stated. This data can be obtained free of charge from CSD for compound {Pd 84 } from CCDC, Cambridge, UK; email deposit@ccdc.cam.ac.uk, CCDC 846615. Thermogravimetric Analysis: TGA was performed on a TA Q500 instrument under a nitrogen atmosphere. UV-Vis spectroscopy: UV-Vis spectra were collected using a JASCO V-670 spectrometer equipped with an ISV723 60mm integrating sphere in diffuse reflectance mode.
2. Syntheses of {Pd 84 } and {Pd 17 } Synthesis of {Pd 84 }: NaH 2 PO 4 -Na 2 HPO 4 solution (22 ml, 0.15 M) at a ph of 6.5-7.1 was added to Pd(OAc) 2 (0.56 g, 2.5mmol). The suspension was left stirring rigorously for 20 hours. The dark red solution was centrifuged and filtered to remove a small amount of solids. The ph of filtration then needed to be checked, and a few drops of 1M NaOH were added to adjust the ph to 4.5. Evaporation of the filtrate from an open beaker led to well-formed reddish long needle crystals after a few days. The crystals were collected by filtration and airdried. Yield: ca. 15-20% (based on Pd); 31 P-NMR (400MHz, D 2 O) δ 22.0, 15.7 ppm; 13 C-NMR (400MHz, D 2 O) δ 187.7, 186.1, 23.55 ppm; IR: 3300, 2300, 2060, 1550, 1510, 1400, 1350, 950, 875, 690 cm -1 ; Elemental analysis, Calc. for C 56 H 498 Na 56 O 466 P 42 Pd 84, C 3.3%, H 2.5, Na 6.4%, P 6.5%, Pd 44.4%; Found C 3.7%, H 1.3%, Na 6.5%, P 6.7%, Pd 44.3%. Synthesis of Na 9 [Pd 2 {H 7 Pd II 15O 10 (PO 4 ) 10 }] ({Pd 17 }) 4 : NaH 2 PO 4 -Na 2 HPO 4 solution at a ph of 6.5 (22 ml, prepared from adding 1M NaOH to 0.15 M solution of NaH 2 PO 4 ) was added to Pd(OAc) 2 (0.56 g, 2.5mmol). The suspension was left stirring rigorously and heating to 85 ºC for 90 min. After the heating, the dark black solution was cooled to room temperature (ph=4.0) and filtered to remove a small amount of black solids. Slow evaporation at room temperature led to some black needle crystals after 2 weeks. The crystals were collected by filtration and air-dried. Yield: ca. 5% (based on Pd). Figure S1: Wire model of the subunit, {Pd 6 }, of the cluster anion {Pd 84 }, which consists of a {Pd 6 (μ 4 -O) 2 } core (blue tetrahedra), two capping PO 4 3-, a μ 2 -O, two CH 3 COO - and a bridging PO 4 3-. Figure S2: Comparison of the Pd-Pd distances in the virtual building blocks of {Pd 6 }. Left: the geometry of the {Pd 6 } metal core. Right: typical distances in each subunit, showing two different types of Pd-Pd: 3.2-3.5 Å (1-5, 7-11) and 2.9 Å (6).
3. MS Studies of {Pd 84 }, {Pd 17 } and the two-component reactions Figure S3: MS spectra of a) Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution without heating (25 C); b) Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution with heating (85 C); c) single crystals of {Pd 84 } in water; and d) single crystals of {Pd 17 } in water.
Figure S4: MS spectrum of the mixture of Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution without heating (25 C), revealing a significant envelope of very high nuclearity highly charged molecules in the mass range of 10-25 kd.
4. Characterization of {Pd 84 }: IR, 13 C/ 1 H/ 31 P-NMR, UV and TGA 100 90 80 %Transmittance 70 60 50 40 30 20 10 0 3600 2600 1600 Wavenumbers (cm -1 ) 600 Figure S5: IR spectrum of {Pd 84 }, showing two sharp characteristic peaks of carboxylate at the wavenumber 1550 and 1440 cm -1.
Figure S6: 13 C-NMR of a) sodium acetate and b) {Pd 84 } in D 2 O. 6 5 4 3 2 1 0 ppm 25 20 15 10 5 0-5 ppm Figure S7: 1 H-NMR and 31 P-NMR of {Pd 84 } in D 2 O
Absorption 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 200 400 600 800 Wavelength Figure S8: UV-Vis spectrum of {Pd 84 } in aqueous solution (0.005 mm). Sample: fx7702 Size: 16.7790 mg Method: Ramp Comment: 10C/min to 800 in N2 100 TGA File: U:\group\Feng Xu\Data\TGA\fx7702.001 Operator: Feng Xu Run Date: 2011-07-06 16:31 Instrument: TGA Q500 V6.7 Build 203 2.0 95 12.42% 1.5 90 Weight (%) 85 80 14.68% 1.0 0.5 Deriv. Weight (%/ C) 75 0.0 70-0.5 0 200 400 600 800 Temperature ( C) Figure S9: TGA plot of {Pd 84 } Universal V4.1D TA Instruments
5. The hypothetical polyoxopalladate cluster, {Pd 60 } Figure S10: The negative ion mass spectrum of the as-prepared {Pd 84 } mother liquid, showing the extreme complexity of the solution with a great number of different highly-charged species. By careful examination of the spectrum, the peak at m/z = 1515.0 can be found and assigned to a 8 - -charged species with the typical formula [(Pd 5 O 5 ) 12 (PO 4 ) 30 H 35 Na 47 (H 2 O) 45 ] 8-. 6. Legend for the movie Figure S11: Still from the movie Pd Conversions (full).avi which shows the hypothetical assembly of the {Pd84} wheel from the {Pd17} and highlights the transferable building blocks. Assembly of the predicted {Pd60} is also shown with reference to the building blocks in the {Pd17}. 7. References (1) Sheldrick G, (2008) A short history of SHELX. Acta Crystallogr., Sect. A: Found. Crystallogr 64: 112-122. (2) Farrugia F, (1999) WinGX Suite for Single Crystal Small Molecule Crystallograph, J. Appl. Crystallogr 32: 837-838. (3) Clark RC, Reid JS, (1995) The analytical calculation of absorption in multifaceted crystals, Acta Crystallogr., Sect. A: Found. Crystallogr 51: 887-897. (4) Cronin L et al. (2011) A Supramolecular Heteropolyoxopalladate {Pd 15 } Cluster Host Encapsulating a {Pd 2 } Dinuclear Guest: [Pd II 2 {H 7 Pd II 15O 10 (PO 4 ) 10 }] 9-. J Am Chem Soc 133(13):4684 4686.